CN104028385A - A kind of preparation method of coal slime flotation accelerator and the method for flotation coal slime - Google Patents
A kind of preparation method of coal slime flotation accelerator and the method for flotation coal slime Download PDFInfo
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- 239000003245 coal Substances 0.000 title claims abstract description 68
- 238000005188 flotation Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 68
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 13
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 14
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 7
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- BVTJGGGYKAMDBN-UHFFFAOYSA-N Dioxetane Chemical compound C1COO1 BVTJGGGYKAMDBN-UHFFFAOYSA-N 0.000 claims 1
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- 230000000694 effects Effects 0.000 description 9
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
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- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- YYEHOLBIXGDEGT-UHFFFAOYSA-N ethenoxyethene;sulfuric acid Chemical compound C=COC=C.OS(O)(=O)=O YYEHOLBIXGDEGT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种煤泥浮选促进剂的制备方法及浮选煤泥的方法，所述的促进剂是以聚合度为n＝4-12的烷基酚聚氧乙烯醚和氨基磺酸为原料，两者的摩尔比为1：0.5～1：0.6之间，控制反应温度为70～90℃，合成过程中，需要不断进行搅拌，反应时间为30～40分钟，反应结束后，降至常温即可；利用促进剂浮选煤泥时，促进剂用量只占捕收剂用量的0.5-2wt％，与单独使用烃油类捕收剂相比，在精煤灰分相当的情况下，精煤产率能够提高2％～3wt％，节油率达到20％～30wt％。不仅有利于节约烃类油捕收剂的用量，还能够优化分选指标，从而整体提高经济效益。The invention discloses a method for preparing a coal slime flotation accelerator and a method for flotation coal slime. The accelerator is an alkylphenol polyoxyethylene ether with a polymerization degree of n=4-12 and aminosulfonic acid As raw materials, the molar ratio of the two is between 1:0.5 and 1:0.6, and the reaction temperature is controlled at 70 to 90°C. During the synthesis process, continuous stirring is required, and the reaction time is 30 to 40 minutes. After the reaction, the drop to normal temperature; when the accelerator is used to flotation coal slime, the amount of the accelerator only accounts for 0.5-2wt% of the amount of the collector. The yield of clean coal can be increased by 2%-3wt%, and the fuel saving rate can reach 20%-30wt%. Not only is it beneficial to save the amount of hydrocarbon oil collector, but it can also optimize the sorting index, thereby improving the overall economic benefit.
Description
技术领域technical field
本发明涉及煤泥浮选助剂，尤其是煤泥浮选用的促进剂。The invention relates to a coal slime flotation aid, in particular to a coal slime flotation accelerator.
背景技术Background technique
浮选是煤泥回收的主要方法，它是依靠煤与矸石表面性质的差异，在气-固-液三相中进行分选。煤泥浮选过程通常需要加入非极性烃类油(如煤油、柴油)作为捕收剂来提高煤粒表面疏水性。煤(柴)油不溶于水，在水中的分散性差，只能以较大“油滴”(>1mm)的形式存在，与煤粒发生接触碰撞并附着的概率较小，同时还会聚集成更大的油滴，因此，煤(柴)油用量较高。加之煤油和柴油多来自石油裂解产品，随着油价上涨，导致选煤成本上升，降低了选煤经济效益。Flotation is the main method of coal slime recovery. It relies on the difference in the surface properties of coal and gangue to separate in the gas-solid-liquid three-phase. Coal slime flotation usually requires the addition of non-polar hydrocarbon oils (such as kerosene, diesel) as collectors to improve the surface hydrophobicity of coal particles. Coal (diesel) oil is insoluble in water and has poor dispersion in water. It can only exist in the form of larger "oil droplets" (>1mm), and the probability of contact, collision and adhesion with coal particles is small, and it will also aggregate into more Large oil droplets, therefore, the amount of coal (diesel) oil is higher. In addition, kerosene and diesel mostly come from petroleum cracking products. As the oil price rises, the cost of coal preparation will increase and the economic benefits of coal preparation will be reduced.
为了提高煤(柴)油等烃油捕收剂在水中的分散能力，一般通过加入促进剂(一般为表面活性剂)来提高它的捕收效果。目前普遍公认的原理在于：一方面降低了油-水的表面张力，改善煤(柴)油的分散性，使其以更细小的“油滴”分散在矿浆中；另一方面，促进剂还可将煤表面局部亲水区域变得疏水，通过表面改性提高煤粒整体的表面疏水性。但实际上，促进剂不仅可将煤表面改性，同样也可以将矸石表面改性，这样就导致实际浮选过程中，虽然促进剂可以降低煤(柴)油的用量并获得较高的精煤产率，但也不可避免的将部分矸石带入精煤产品中，造成精煤灰分较高，大大影响了精煤产品质量。In order to improve the dispersibility of coal (diesel) oil and other hydrocarbon oil collectors in water, generally by adding accelerators (usually surfactants) to improve its collection effect. The currently generally accepted principle is: on the one hand, it reduces the surface tension of oil-water, improves the dispersibility of coal (diesel) oil, and makes it dispersed in the pulp with finer "oil droplets"; on the other hand, the accelerator also The local hydrophilic area on the coal surface can be made hydrophobic, and the overall surface hydrophobicity of coal particles can be improved through surface modification. But in fact, the accelerator can not only modify the surface of coal, but also modify the surface of gangue, which leads to the fact that in the actual flotation process, although the accelerator can reduce the amount of coal (diesel) oil and obtain a higher refined Coal production rate, but it is also inevitable that part of gangue will be brought into clean coal products, resulting in high ash content of clean coal, which greatly affects the quality of clean coal products.
烷基酚聚氧乙烯醚是一种非离子型表面活性剂，目前被本领域的技术人员普遍作为煤泥浮选促进剂以占煤(柴)油5％-20％的比例使用，由于其表面活性剂的特点，也不可避免的存在对矸石的无选择性表面改性，导致精煤灰分普遍偏高。为了克服烷基酚聚氧乙烯醚作为煤泥浮选促进剂的缺陷，目前采取的措施一般是对烷基酚聚氧乙烯醚进行改性，改性方法是：以烷基酚聚氧乙烯醚为原料，选用合适的硫酸化试剂-氨基磺酸和催化剂，在高温高压条件下，进行酯化反应，得到兼有非离子表面活性剂和阴离子表面活性剂优点的烷基酚聚氧乙烯醚衍生物--烷基酚聚氧乙烯醚硫酸盐，或者在反应结束后用氢氧化钠进一步中和，得到烷基酚聚氧乙烯醚硫酸钠。比如中国专利公开号CN101328141A公开的一种烷基酚聚氧乙烯醚硫酸钠的制备方法，它以烷基酚聚氧乙烯醚与氨基磺酸为原料，在有烷基或芳基取代的脲类化合物作为催化剂的条件下进行酯化反应，烷基酚聚氧乙烯醚，氨基磺酸与催化剂的摩尔比为1∶1～1.2∶0.1，酯化反应温度为110～130℃，反应时间60～120分钟。酯化反应结束后用氢氧化钠中和酯化反应产物烷基酚聚氧乙烯醚硫酸铵，最终取得产品烷基酚聚氧乙烯醚硫酸钠。Alkylphenol polyoxyethylene ether is a kind of nonionic surface active agent, is generally used as coal slime flotation accelerator by those skilled in the art at present to account for the ratio of 5%-20% of coal (diesel) oil, because its Due to the characteristics of surfactants, there is also the inevitable non-selective surface modification of gangue, resulting in generally high ash content in clean coal. In order to overcome the defects of alkylphenol polyoxyethylene ether as a coal slime flotation accelerator, the measures currently taken are generally to modify the alkylphenol polyoxyethylene ether. The modification method is: use alkylphenol polyoxyethylene ether As a raw material, select a suitable sulfamic acid-sulfamic acid and catalyst, and carry out esterification reaction under high temperature and high pressure conditions to obtain an alkylphenol polyoxyethylene ether derivative with the advantages of both nonionic surfactants and anionic surfactants. Substance--alkylphenol polyoxyethylene ether sulfate, or further neutralized with sodium hydroxide after the reaction to obtain sodium alkylphenol polyoxyethylene ether sulfate. Such as Chinese patent publication number CN101328141A discloses a kind of preparation method of alkylphenol polyoxyethylene ether sodium sulfate, it is raw material with alkylphenol polyoxyethylene ether and sulfamic acid, in the urea class that has alkyl or aryl substitution The esterification reaction is carried out under the condition that the compound is used as a catalyst, the molar ratio of alkylphenol polyoxyethylene ether, sulfamic acid to the catalyst is 1:1～1.2:0.1, the esterification reaction temperature is 110～130°C, and the reaction time is 60～ 120 minutes. After the esterification reaction is finished, sodium hydroxide is used to neutralize the product of the esterification reaction, ammonium alkylphenol polyoxyethylene ether, to finally obtain the product sodium alkylphenol polyoxyethylene ether sulfate.
上述方法存在的缺陷是：在对烷基酚聚氧乙烯醚进行改性时，本领域技术人员仅考虑了烷基酚聚氧乙烯醚的转化率，为了提高烷基酚聚氧乙烯醚的转化率，人为提高反应温度，延长反应时间，并利用催化剂促进反应，最终得到烷基酚聚氧乙烯醚硫酸钠。烷基酚聚氧乙烯醚硫酸钠是阴离子型表面活性剂，在矿浆中带负电，与带负电的矸石颗粒表面相排斥，在矸石颗粒表面吸附后改性的强度远小于烷基酚聚氧乙烯醚，有利于改善浮选过程中对矸石的无选择性捕收。但烷基酚聚氧乙烯醚硫酸钠与烷基酚聚氧乙烯醚相比，临界胶束浓度(CMC)一般高3-4倍，大幅度提高的临界胶束浓度(CMC)导致烷基酚聚氧乙烯醚硫酸钠降低油-水表面张力的效率急剧降低，不利于改善煤(柴)油的分散性以及节约其用量；另外，为了追求高转化率所采取的一系列技术措施使得合成成本高，合成工艺复杂。The defect that the above-mentioned method exists is: when carrying out modification to alkylphenol polyoxyethylene ether, those skilled in the art only considered the conversion ratio of alkylphenol polyoxyethylene ether, in order to improve the conversion of alkylphenol polyoxyethylene ether rate, artificially increase the reaction temperature, prolong the reaction time, and use a catalyst to promote the reaction, and finally obtain sodium alkylphenol polyoxyethylene ether sulfate. Alkylphenol polyoxyethylene ether sodium sulfate is an anionic surfactant, which is negatively charged in the pulp and repelled from the surface of negatively charged gangue particles. The strength of modification after adsorption on the surface of gangue particles is much smaller than that of alkylphenol polyoxyethylene Ether is beneficial to improve the non-selective collection of gangue in the flotation process. However, compared with alkylphenol polyoxyethylene ether, the critical micelle concentration (CMC) of alkylphenol polyoxyethylene ether sodium sulfate is generally 3-4 times higher, and the greatly improved critical micelle concentration (CMC) causes alkylphenol Sodium polyoxyethylene ether sulfate reduces the efficiency of oil-water surface tension sharply, which is not conducive to improving the dispersion of coal (diesel) oil and saving its consumption; in addition, a series of technical measures taken in order to pursue high conversion rate make the synthesis cost High, complex synthesis process.
发明内容Contents of the invention
为了同时克服烷基酚聚氧乙烯醚促进剂容易造成精煤灰分较高，大大影响精煤产品质量，以及烷基酚聚氧乙烯醚硫酸钠促进剂合成成本高、合成工序复杂、在浮选煤泥时对烃类油的分散效果差、烃类油捕收剂用量大的技术缺陷，同时保留二者优点，本发明提供一种煤泥浮选促进剂的制备方法。In order to overcome the high ash content of clean coal caused by alkylphenol polyoxyethylene ether accelerators, which greatly affects the quality of clean coal products, and the high synthesis cost and complex synthesis process of alkylphenol polyoxyethylene ether sodium sulfate accelerators in flotation Coal slime has the technical defects of poor dispersion effect on hydrocarbon oil and large amount of hydrocarbon oil collector, while retaining the advantages of both. The invention provides a preparation method of a coal slime flotation accelerator.
本发明同时提供浮选煤泥的方法。The invention also provides a method for flotation coal slime.
为达到上述目的，本发明煤泥浮选促进剂的制备方法是：以烷基酚聚氧乙烯醚(氧化乙烯的聚合度为n＝4-12)和氨基磺酸为原料，两者的摩尔比为1：0.5～1：0.6之间，控制反应温度为70～90℃，合成过程中，需要不断进行搅拌，反应时间为30～40分钟，反应结束后，降至常温即可，烷基酚聚氧乙烯醚的转化率一般为40～50％，反应结束后得到的产物包括烷基酚聚氧乙烯醚和合成的烷基酚聚氧乙烯醚硫酸铵，且以1.5：1～1：1的摩尔比例共存。In order to achieve the above object, the preparation method of the coal slime flotation accelerator of the present invention is: take alkylphenol polyoxyethylene ether (the degree of polymerization of oxyethylene is n=4-12) and aminosulfonic acid as raw material, the mole of both The ratio is between 1:0.5 and 1:0.6, and the reaction temperature is controlled at 70-90°C. During the synthesis process, continuous stirring is required, and the reaction time is 30-40 minutes. The conversion rate of phenol polyoxyethylene ether is generally 40-50%. After the reaction, the products obtained include alkylphenol polyoxyethylene ether and synthesized alkylphenol polyoxyethylene ether ammonium sulfate, and the ratio is 1.5:1~1: A molar ratio of 1 coexists.
本发明浮选煤泥的方法是：The method for flotation coal slime of the present invention is:
第一步：按照上述方法制备促进剂The first step: prepare the accelerator according to the above method
第二步：设置两个搅拌桶，分别称为一段搅拌桶和二段搅拌桶，一段搅拌桶布置在高位，二段搅拌桶布置在低位，矿浆可从一段搅拌桶自流进入二段搅拌桶。Step 2: Set up two mixing tanks, called the first mixing tank and the second mixing tank respectively. The first mixing tank is arranged at a high position, and the second mixing tank is arranged at a low position. The ore pulp can flow into the second mixing tank from the first mixing tank.
第三步：从分选系统来的煤泥水先进入一段搅拌桶，然后向一段搅拌桶中加入第一步制备的促进剂，要求促进剂的加入量为2～24g/t干煤泥，保证1分钟以上的搅拌混匀时间，搅拌机转速2000～2800r/min；Step 3: The coal slime water from the sorting system first enters the first section of the mixing tank, and then adds the accelerator prepared in the first step into the first section of the mixing bucket. The addition of the accelerator is required to be 2-24g/t of dry coal slime to ensure Stirring and mixing time of more than 1 minute, the speed of the mixer is 2000-2800r/min;
第四步：将第三步混匀促进剂的煤泥水自流到二段搅拌桶，同时在二段搅拌桶加入烃类油捕收剂和起泡剂，保证1分钟以上的搅拌混匀时间，要求烃类油类捕收剂的加入量为0.4～1.2kg/t干煤泥，起泡剂用量为0.04～0.12kg/t干煤泥，搅拌机转速2000～2800r/min；Step 4: Self-flow the slime water of the mixing accelerator in the third step to the second-stage mixing tank, and at the same time add hydrocarbon oil collector and foaming agent to the second-stage mixing tank to ensure a stirring and mixing time of more than 1 minute. It is required that the amount of hydrocarbon oil collector added is 0.4-1.2kg/t dry coal slime, the amount of foaming agent is 0.04-0.12kg/t dry coal slime, and the speed of the mixer is 2000-2800r/min;
第五步：将第四步形成的混合物进入浮选机进行浮选即可。The fifth step: Put the mixture formed in the fourth step into the flotation machine for flotation.
本发明的促进剂的作用机理是：The mechanism of action of accelerator of the present invention is:
本发明促进剂有两种成分，分别是烷基酚聚氧乙烯醚和烷基酚聚氧乙烯醚硫酸铵，以摩尔比1.5：1～1：1比例构成的，这两种成分通过协同作用，能够使促进剂的临界胶束浓度(CMC)低于烷基酚聚氧乙烯醚和烷基酚聚氧乙烯醚硫酸铵各自独立体系的临界胶束浓度(CMC)，高效降低油-水界面张力，大大提高烃油在水中的分散性，形成细小的“油滴”(1×10-3～0.5mm)，大幅度降低烃类油捕收剂的用量；另外，借助烷基酚聚氧乙烯醚硫酸铵与带负电的矸石颗粒之间的排斥作用，减少了本发明促进剂在使用过程中对矸石的无选择性捕收作用。The accelerator of the present invention has two components, which are alkylphenol polyoxyethylene ether and alkylphenol polyoxyethylene ether ammonium sulfate, and are composed of a molar ratio of 1.5:1 to 1:1. , can make the critical micelle concentration (CMC) of the accelerator lower than the critical micelle concentration (CMC) of the independent system of alkylphenol polyoxyethylene ether and alkylphenol polyoxyethylene ether ammonium sulfate, and effectively reduce the oil-water interface Tension, greatly improving the dispersibility of hydrocarbon oil in water, forming fine "oil droplets" (1×10 -3 ~0.5mm), greatly reducing the amount of hydrocarbon oil collector; in addition, with the help of alkylphenol polyoxygen The repulsion between ammonium vinyl ether sulfate and negatively charged gangue particles reduces the non-selective collection of gangue by the accelerator of the present invention during use.
下面说明本发明的优点：The advantages of the present invention are illustrated below:
在本领域公知常识中，烷基酚聚氧乙烯醚改性后具有改善捕收剂的捕收能力，改性过程中原料的转化率越高，得到的产物越纯，有效成分含量越多，浮选煤泥时用的量就会降低，这不但是本领域技术人员也是别的领域的认知，基于这一传统思维束缚，引导本领域技术人员在对烷基酚聚氧乙烯醚进行改性时，想法设法提高烷基酚聚氧乙烯醚的转化率，为了提高烷基酚聚氧乙烯醚的转化率，不惜提高反应温度、反应时间和压力，没有人去想其他方面的可能性。本发明人克服了这种技术偏见，提出了一种与以往技术构思完全不同的技术方案，大胆降低烷基酚聚氧乙烯醚改性温度和时间，从而降低烷基酚聚氧乙烯醚的转化率，使得改性后的成分体系中，烷基酚聚氧乙烯醚和烷基酚聚氧乙烯醚硫酸铵处于一个最适合改善捕收剂捕收性能的最佳配比，在最佳配比条件下，烷基酚聚氧乙烯醚对烷基酚聚氧乙烯醚硫酸铵的协同作用远远大于它本身可能带来的缺陷，从而在临界胶束浓度下获得最低表面张力，达到高效降低油-水界面张力，提高烃油在水中的分散性。并且使得促进剂以及煤泥浮选的成本大大降低，另外，也免去了操作人员在浮选煤泥时要加多个表面活性剂的程序，可大规模应用于工业生产。In the common knowledge in this field, the modified alkylphenol polyoxyethylene ether can improve the collection ability of the collector, the higher the conversion rate of the raw material in the modification process, the purer the obtained product, and the more active ingredients. The amount used in flotation coal slime will be reduced, which is not only the cognition of those skilled in the art but also in other fields. Based on the constraints of this traditional thinking, it guides those skilled in the art to improve In order to increase the conversion rate of alkylphenol polyoxyethylene ether, the reaction temperature, reaction time and pressure are increased, and no one thinks about other possibilities. The inventor overcomes this technical prejudice and proposes a technical solution completely different from the previous technical concept, boldly reducing the modification temperature and time of alkylphenol polyoxyethylene ether, thereby reducing the conversion of alkylphenol polyoxyethylene ether rate, so that in the modified component system, the alkylphenol polyoxyethylene ether and the alkylphenol polyoxyethylene ether ammonium sulfate are in an optimal ratio that is most suitable for improving the collection performance of the collector. Under certain conditions, the synergistic effect of alkylphenol polyoxyethylene ether on ammonium sulfate of alkylphenol polyoxyethylene ether is far greater than the defects it may bring, so that the lowest surface tension can be obtained at the critical micelle concentration, and the oil can be effectively reduced. -Water interfacial tension, improving the dispersibility of hydrocarbon oil in water. And the cost of accelerator and coal slime flotation is greatly reduced. In addition, it also eliminates the need for operators to add multiple surfactants when flotation coal slime, and can be applied to industrial production on a large scale.
利用本专利提供的浮选促进剂进行煤泥浮选时，在一段搅拌桶中加入促进剂，通过搅拌作用首先使促进剂在矿浆中得到高效分散，不仅获得较低的界面张力，同时也能对煤泥表面的局部亲水区域进行改性，为后续烃油捕收剂的作用创造良好的环境；二段搅拌桶中加入烃油捕收剂和起泡剂，在较低的界面张力条件下，通过搅拌作用，烃油捕收剂将会被高效分散成极细的“油滴”，从而最终提高煤泥浮选效率。本发明促进剂用量只占捕收剂用量的0.5-2wt％，与单独使用烃油类捕收剂相比，在精煤灰分相当的情况下，精煤产率能够提高2％～3wt％，节油率达到20％～30wt％。不仅有利于节约烃类油捕收剂的用量，还能够优化分选指标，从而整体提高经济效益。When the flotation accelerator provided by this patent is used for coal slime flotation, the accelerator is added to the first stage of the mixing tank, and the accelerator is firstly dispersed efficiently in the pulp through stirring, which not only obtains a lower interfacial tension, but also can Modify the local hydrophilic area on the surface of the coal slime to create a good environment for the subsequent action of hydrocarbon oil collectors; add hydrocarbon oil collectors and foaming agents to the second-stage mixing tank, under the condition of low interfacial tension Under the action of agitation, the hydrocarbon oil collector will be efficiently dispersed into extremely fine "oil droplets", thereby ultimately improving the efficiency of coal slime flotation. The amount of the accelerant of the present invention only accounts for 0.5-2wt% of the amount of the collector. Compared with the single use of the hydrocarbon oil collector, the yield of the clean coal can be increased by 2%-3wt% when the ash content of the clean coal is equivalent. The fuel saving rate reaches 20%-30wt%. Not only is it beneficial to save the amount of hydrocarbon oil collector, but it can also optimize the sorting index, thereby improving the overall economic benefit.
为了证明本发明浮选效果好、成本低的优点，在达到同样的浮选效果下，将本发明方法制备的促进剂效果与其他三个对照组进行比较，其中对照组1是没有加入促进剂的效果，对照组2是按照现有方法制备的促进剂效果；对照组3是利用烷基酚聚氧乙烯醚和烷基酚聚氧乙烯醚硫酸铵复配的促进剂效果。在试验时，分别用可浮性较好和较差的两种煤泥作为实验对象，试验结果分别见表一和表二。In order to prove the advantages of good flotation effect and low cost of the present invention, under the same flotation effect, the accelerator effect prepared by the method of the present invention is compared with other three control groups, wherein control group 1 does not add accelerator The effect of the control group 2 is the effect of the accelerator prepared according to the existing method; the control group 3 is the effect of the accelerator compounded with alkylphenol polyoxyethylene ether and alkylphenol polyoxyethylene ether ammonium sulfate. In the test, two kinds of coal slime with better floatability and poorer floatability were used as the test objects, and the test results are shown in Table 1 and Table 2 respectively.
表一 可浮性较好煤泥Table 1 Coal slime with good floatability
表二 可浮性较差煤泥Table 2 Coal slime with poor floatability
上述对比实验中，本发明促进剂合成过程中烷基酚聚氧乙烯醚的转化率按45％计算，则产物中烷基酚聚氧乙烯醚和合成的烷基酚聚氧乙烯醚硫酸铵的摩尔比为1.22：1，为了便于比较，对照组3的烷基酚聚氧乙烯醚和烷基酚聚氧乙烯醚硫酸铵的复配比例也定为1.22：1。In the above-mentioned comparison experiment, the conversion ratio of alkylphenol polyoxyethylene ether in the promotor synthesis process of the present invention is calculated by 45%, and then the alkylphenol polyoxyethylene ether and synthetic alkylphenol polyoxyethylene ether ammonium sulfate in the product The molar ratio is 1.22:1. For the convenience of comparison, the compounding ratio of alkylphenol polyoxyethylene ether and alkylphenol polyoxyethylene ether ammonium sulfate in control group 3 is also set at 1.22:1.
上述表中成本核算依据：柴油按7400元/吨计算，现有方法制备的促进剂(烷基酚聚氧乙烯醚硫酸钠)按15000元/吨计算，烷基酚聚氧乙烯醚和烷基酚聚氧乙烯醚硫酸铵复配的促进剂按12000元/吨计算，本发明制备的促进剂按11000元/吨计算。The cost calculation basis in the above table is: diesel oil is calculated at 7,400 yuan/ton, the accelerator (alkylphenol polyoxyethylene ether sodium sulfate) prepared by the existing method is calculated at 15,000 yuan/ton, alkylphenol polyoxyethylene ether and alkyl The accelerator compounded with phenol polyoxyethylene ether ammonium sulfate is calculated at 12,000 yuan/ton, and the accelerator prepared by the present invention is calculated at 11,000 yuan/ton.
从上述表中数据分析可以看出：From the data analysis in the above table, it can be seen that:
本发明与对照组2和3相比：在同样添加促进剂的情况下，无论是浮选较好的煤泥还是浮选较差煤泥，在浮选效果相当的前提下，本发明不但促进剂用量大大低于对照组2和3，并且捕收剂柴油的用量明显降低，从而使浮选成本明显低于对照组2和3。The present invention compares with control group 2 and 3: under the same situation of adding accelerator, no matter it is coal slime with better flotation or poor coal slime with flotation, under the premise that the flotation effect is equivalent, the present invention not only promotes The amount of agent used is much lower than that of control groups 2 and 3, and the amount of collector diesel oil is significantly reduced, so that the cost of flotation is significantly lower than that of control groups 2 and 3.
本发明和对照组1相比，本发明虽然添加了促进剂，但是，浮选成本并没有因此而提高，这是由于添加促进剂以后捕收剂柴油的用量降低了；而且在精煤灰分相当的情况下，在浮选较好煤泥时，精煤产率能够提高2.53wt％，节油率达到25.8wt％；在浮选较差煤泥时，精煤产率能够提高2.75wt％，节油率达到21.5wt％。The present invention compares with matched group 1, although the present invention has added promotor, flotation cost does not therefore improve, and this is because the consumption of collector diesel oil has reduced after adding promotor; In the case of better flotation, the clean coal yield can be increased by 2.53wt%, and the oil saving rate can reach 25.8wt%; when the flotation is poor, the clean coal yield can be increased by 2.75wt%, The fuel saving rate reaches 21.5wt%.
具体实施方式Detailed ways
下面通过具体实施例进一步说明本发明的技术方案。The technical solution of the present invention is further illustrated below through specific examples.
实施例一：Embodiment one:
以烷基酚聚氧乙烯醚(氧化乙烯的聚合度为n＝4-12)和氨基磺酸为原料，两者的摩尔比为1：0.5，控制反应温度为70℃，合成过程中，需要不断进行搅拌，反应时间为30分钟，反应结束后，降至常温即可，烷基酚聚氧乙烯醚的转化率为40.86％，反应结束后得到的产物包括烷基酚聚氧乙烯醚和合成的烷基酚聚氧乙烯醚硫酸铵，且以1.45：1的摩尔比例共存。Alkylphenol polyoxyethylene ether (the degree of polymerization of ethylene oxide is n=4-12) and sulfamic acid are used as raw materials, the molar ratio of the two is 1:0.5, and the reaction temperature is controlled at 70°C. During the synthesis process, it is necessary Stir continuously, and the reaction time is 30 minutes. After the reaction, it can be lowered to normal temperature. The conversion rate of alkylphenol polyoxyethylene ether is 40.86%. The products obtained after the reaction include alkylphenol polyoxyethylene ether and synthetic Alkylphenol polyoxyethylene ether ammonium sulfate, and coexist in a molar ratio of 1.45:1.
在浮选煤泥时，减少烃类油捕收剂用量23.71wt％，加入的促进剂占烃类油的0.9wt％。During flotation of coal slime, the amount of hydrocarbon oil collector is reduced by 23.71wt%, and the accelerant added accounts for 0.9wt% of hydrocarbon oil.
实施例二：Embodiment two:
以烷基酚聚氧乙烯醚(氧化乙烯的聚合度为n＝4-12)和氨基磺酸为原料，两者的摩尔比为1：0.55，控制反应温度为80℃，合成过程中，需要不断进行搅拌，反应时间为35分钟，反应结束后，降至常温即可，烷基酚聚氧乙烯醚的转化率为45.62％，反应结束后得到的产物包括烷基酚聚氧乙烯醚和合成的烷基酚聚氧乙烯醚硫酸铵，且以1.2：1的摩尔比例共存。Alkylphenol polyoxyethylene ether (the degree of polymerization of ethylene oxide is n=4-12) and sulfamic acid are used as raw materials, the molar ratio of the two is 1:0.55, and the reaction temperature is controlled at 80°C. During the synthesis process, it is necessary to Stir continuously, and the reaction time is 35 minutes. After the reaction is completed, it can be lowered to normal temperature. The conversion rate of alkylphenol polyoxyethylene ether is 45.62%. The products obtained after the reaction include alkylphenol polyoxyethylene ether and synthetic Alkylphenol polyoxyethylene ether ammonium sulfate, and coexist in a molar ratio of 1.2:1.
在浮选煤泥时，减少烃类油捕收剂用量25.77wt％，加入的促进剂占烃类油的1.1wt％。When flotation coal slime, the amount of hydrocarbon oil collector is reduced by 25.77wt%, and the accelerant added accounts for 1.1wt% of hydrocarbon oil.
实施例三：Embodiment three:
以烷基酚聚氧乙烯醚(氧化乙烯的聚合度为n＝4-12)和氨基磺酸为原料，两者的摩尔比为1：0.6，控制反应温度为90℃，合成过程中，需要不断进行搅拌，反应时间为40分钟，反应结束后，降至常温即可，烷基酚聚氧乙烯醚的转化率为49.21％，反应结束后得到的产物包括烷基酚聚氧乙烯醚和合成的烷基酚聚氧乙烯醚硫酸铵，且以1.03：1的摩尔比例共存；Alkylphenol polyoxyethylene ether (the degree of polymerization of ethylene oxide is n=4-12) and sulfamic acid are used as raw materials, the molar ratio of the two is 1:0.6, and the reaction temperature is controlled at 90°C. During the synthesis process, it is necessary Stir continuously, and the reaction time is 40 minutes. After the reaction, it can be lowered to normal temperature. The conversion rate of alkylphenol polyoxyethylene ether is 49.21%. The products obtained after the reaction include alkylphenol polyoxyethylene ether and synthetic Alkylphenol polyoxyethylene ether ammonium sulfate, and coexist in a molar ratio of 1.03:1;
在浮选煤泥时，减少烃类油捕收剂用量21.36wt％，加入的促进剂占烃类油的1.5wt％。During the flotation of coal slime, the amount of hydrocarbon oil collector is reduced by 21.36wt%, and the accelerator added accounts for 1.5wt% of hydrocarbon oil.
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